JP2009298771A - Method for producing 2-alkyl-2-cycloalken-1-one - Google Patents
Method for producing 2-alkyl-2-cycloalken-1-one Download PDFInfo
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- JP2009298771A JP2009298771A JP2009089799A JP2009089799A JP2009298771A JP 2009298771 A JP2009298771 A JP 2009298771A JP 2009089799 A JP2009089799 A JP 2009089799A JP 2009089799 A JP2009089799 A JP 2009089799A JP 2009298771 A JP2009298771 A JP 2009298771A
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- Prior art keywords
- acid
- reaction
- alkyl
- volume
- concentration
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002253 acid Substances 0.000 claims abstract description 36
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000018044 dehydration Effects 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 32
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical group C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 30
- DYVAUIYAEICDNS-UHFFFAOYSA-N 2-(1-hydroxypentyl)cyclopentan-1-one Chemical compound CCCCC(O)C1CCCC1=O DYVAUIYAEICDNS-UHFFFAOYSA-N 0.000 description 28
- 239000011973 solid acid Substances 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 23
- 239000007789 gas Substances 0.000 description 21
- ILHZVKAXFCDFMT-UHFFFAOYSA-N 2-pentylcyclopent-2-en-1-one Chemical compound CCCCCC1=CCCC1=O ILHZVKAXFCDFMT-UHFFFAOYSA-N 0.000 description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 15
- 235000011007 phosphoric acid Nutrition 0.000 description 15
- 239000007795 chemical reaction product Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 11
- 239000006227 byproduct Substances 0.000 description 11
- 229910052763 palladium Inorganic materials 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 125000004429 atom Chemical group 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- VNWOJVJCRAHBJJ-UHFFFAOYSA-N 2-pentylcyclopentan-1-one Chemical compound CCCCCC1CCCC1=O VNWOJVJCRAHBJJ-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 238000007664 blowing Methods 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 150000001721 carbon Chemical group 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 150000007522 mineralic acids Chemical class 0.000 description 6
- 150000007524 organic acids Chemical class 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 125000000962 organic group Chemical group 0.000 description 5
- -1 phosphonic monoester Chemical compound 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 125000001118 alkylidene group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- 0 *C(*)(C(C*C1)C1=O)O Chemical compound *C(*)(C(C*C1)C1=O)O 0.000 description 2
- SVJDZZNVAWQECS-UHFFFAOYSA-N 2-(1-hydroxybutyl)cyclopentan-1-one Chemical compound CCCC(O)C1CCCC1=O SVJDZZNVAWQECS-UHFFFAOYSA-N 0.000 description 2
- BVJDBUQKHVIFPW-UHFFFAOYSA-N 2-(1-hydroxyhexyl)cyclopentan-1-one Chemical compound CCCCCC(O)C1CCCC1=O BVJDBUQKHVIFPW-UHFFFAOYSA-N 0.000 description 2
- YOGOAULRGOSTPO-UHFFFAOYSA-N 2-(1-hydroxypropyl)cyclopentan-1-one Chemical compound CCC(O)C1CCCC1=O YOGOAULRGOSTPO-UHFFFAOYSA-N 0.000 description 2
- LQANWSYLRLMKDX-UHFFFAOYSA-N 2-butylcyclopent-2-en-1-one Chemical compound CCCCC1=CCCC1=O LQANWSYLRLMKDX-UHFFFAOYSA-N 0.000 description 2
- VGECIEOJXLMWGO-UHFFFAOYSA-N 2-hexylcyclopent-2-en-1-one Chemical compound CCCCCCC1=CCCC1=O VGECIEOJXLMWGO-UHFFFAOYSA-N 0.000 description 2
- OCFRCAFXNXHIIX-UHFFFAOYSA-N 2-propylcyclopent-2-en-1-one Chemical compound CCCC1=CCCC1=O OCFRCAFXNXHIIX-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 238000009489 vacuum treatment Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- HEYSXOJTHNPDFR-UHFFFAOYSA-N 2-(1-hydroxy-2-methylbutyl)cyclohexan-1-one Chemical compound CCC(C)C(O)C1CCCCC1=O HEYSXOJTHNPDFR-UHFFFAOYSA-N 0.000 description 1
- RVFBVIPIGOHMKY-UHFFFAOYSA-N 2-(1-hydroxy-2-methylbutyl)cyclopentan-1-one Chemical compound CCC(C)C(O)C1CCCC1=O RVFBVIPIGOHMKY-UHFFFAOYSA-N 0.000 description 1
- BATWHICBOTVWLT-UHFFFAOYSA-N 2-(1-hydroxybutyl)cyclohexan-1-one Chemical compound CCCC(O)C1CCCCC1=O BATWHICBOTVWLT-UHFFFAOYSA-N 0.000 description 1
- AERVJOBGBMEFDV-UHFFFAOYSA-N 2-(1-hydroxycyclohexyl)cyclohexan-1-one Chemical compound C1CCCC(=O)C1C1(O)CCCCC1 AERVJOBGBMEFDV-UHFFFAOYSA-N 0.000 description 1
- YHVIXIKWMNCACN-UHFFFAOYSA-N 2-(1-hydroxycyclohexyl)cyclopentan-1-one Chemical compound C1CCC(=O)C1C1(O)CCCCC1 YHVIXIKWMNCACN-UHFFFAOYSA-N 0.000 description 1
- ALHMNSXTZFDENC-UHFFFAOYSA-N 2-(1-hydroxycyclopentyl)cyclohexan-1-one Chemical compound C1CCCC(=O)C1C1(O)CCCC1 ALHMNSXTZFDENC-UHFFFAOYSA-N 0.000 description 1
- UPGJEXJIJFSFDQ-UHFFFAOYSA-N 2-(1-hydroxycyclopentyl)cyclopentan-1-one Chemical compound C1CCC(=O)C1C1(O)CCCC1 UPGJEXJIJFSFDQ-UHFFFAOYSA-N 0.000 description 1
- LNLPVDYFWHIFTK-UHFFFAOYSA-N 2-(1-hydroxyhexyl)cyclohexan-1-one Chemical compound CCCCCC(O)C1CCCCC1=O LNLPVDYFWHIFTK-UHFFFAOYSA-N 0.000 description 1
- FTIZNBJLOWVDBR-UHFFFAOYSA-N 2-(1-hydroxypentyl)cyclohexan-1-one Chemical compound CCCCC(O)C1CCCCC1=O FTIZNBJLOWVDBR-UHFFFAOYSA-N 0.000 description 1
- RFFJGNBKNOWRDB-UHFFFAOYSA-N 2-(1-hydroxypropyl)cyclohexan-1-one Chemical compound CCC(O)C1CCCCC1=O RFFJGNBKNOWRDB-UHFFFAOYSA-N 0.000 description 1
- JFKJHXNYVRENKI-UHFFFAOYSA-N 2-(2-hydroxypentan-2-yl)cyclohexan-1-one Chemical compound CCCC(C)(O)C1CCCCC1=O JFKJHXNYVRENKI-UHFFFAOYSA-N 0.000 description 1
- DHSKBFPNMAHZNK-UHFFFAOYSA-N 2-(2-hydroxypentan-2-yl)cyclopentan-1-one Chemical compound CCCC(C)(O)C1CCCC1=O DHSKBFPNMAHZNK-UHFFFAOYSA-N 0.000 description 1
- YASHLDRLPYYKRR-UHFFFAOYSA-N 2-(2-methylbutyl)cyclopent-2-en-1-one Chemical compound CCC(C)CC1=CCCC1=O YASHLDRLPYYKRR-UHFFFAOYSA-N 0.000 description 1
- SJDUBHUSYWCGAU-UHFFFAOYSA-N 2-butylcyclohex-2-en-1-one Chemical compound CCCCC1=CCCCC1=O SJDUBHUSYWCGAU-UHFFFAOYSA-N 0.000 description 1
- QYEWYVTZQUZTAQ-UHFFFAOYSA-N 2-cyclohexylcyclohex-2-en-1-one Chemical compound O=C1CCCC=C1C1CCCCC1 QYEWYVTZQUZTAQ-UHFFFAOYSA-N 0.000 description 1
- UHLWJAVICBHQMF-UHFFFAOYSA-N 2-cyclohexylcyclopent-2-en-1-one Chemical compound O=C1CCC=C1C1CCCCC1 UHLWJAVICBHQMF-UHFFFAOYSA-N 0.000 description 1
- KXRIWOPMFJDKDE-UHFFFAOYSA-N 2-cyclopentylcyclohex-2-en-1-one Chemical compound O=C1CCCC=C1C1CCCC1 KXRIWOPMFJDKDE-UHFFFAOYSA-N 0.000 description 1
- IAHUXRDIKWJXQM-UHFFFAOYSA-N 2-cyclopentylcyclopent-2-en-1-one Chemical compound O=C1CCC=C1C1CCCC1 IAHUXRDIKWJXQM-UHFFFAOYSA-N 0.000 description 1
- OLCWJBHILXUEIX-UHFFFAOYSA-N 2-hexylcyclohex-2-en-1-one Chemical compound CCCCCCC1=CCCCC1=O OLCWJBHILXUEIX-UHFFFAOYSA-N 0.000 description 1
- WLAMNBDJUVNPJU-UHFFFAOYSA-M 2-methylbutyrate Chemical compound CCC(C)C([O-])=O WLAMNBDJUVNPJU-UHFFFAOYSA-M 0.000 description 1
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Abstract
Description
本発明は、２−アルキル−２−シクロアルケン−１−オンの製造方法に関する。 The present invention relates to a method for producing 2-alkyl-2-cycloalkene-1-one.
２−アルキル−２−シクロアルケン−１−オンは、生理活性物質や香料の合成中間体として有用である。従来、２−アルキル−２−シクロアルケン−１−オンは、２−（１−ヒドロキシアルキル）シクロアルカノンの脱水反応によって、まず２−（アルキリデン）シクロアルカノンを合成し、次いでこれを異性化反応させることにより製造されている。
上記の脱水反応は、一般的に酸の存在下で行われることが知られており、例えば、特許文献１及び２には、シュウ酸やリン酸を用いた脱水反応が記載され、特許文献３には、固体酸を用いた脱水反応が記載されている。
上記の異性化反応は、金属触媒を用いる例が報告されており、例えば、特許文献４には、白金族金属触媒を用いた異性化反応が記載されている。
2-Alkyl-2-cycloalkene-1-one is useful as a synthetic intermediate for physiologically active substances and fragrances. Conventionally, 2-alkyl-2-cycloalkene-1-one is synthesized by firstly synthesizing 2- (alkylidene) cycloalkanone by dehydration reaction of 2- (1-hydroxyalkyl) cycloalkanone, and then isomerizing it. It is manufactured by reacting.
It is known that the above dehydration reaction is generally performed in the presence of an acid. For example, Patent Documents 1 and 2 describe a dehydration reaction using oxalic acid or phosphoric acid. Describes a dehydration reaction using a solid acid.
Examples of the isomerization reaction using a metal catalyst have been reported. For example, Patent Document 4 discloses an isomerization reaction using a platinum group metal catalyst.
また、脱水反応及び異性化反応を一段階で行う方法も知られている。例えば、特許文献１には、還流ｎ−ブタノール中、塩化水素又は臭化水素を用いて、脱水と異性化とを一段階で行う方法、特許文献５には、不活性溶媒存在下、ハロゲン化水素やスルホン酸類を用いて、系外に水を除去しながら反応を行う方法、特許文献６には、高沸点溶媒存在下スルホン酸類を用いて生成する水及び２−アルキル−２−シクロペンテノンを系外に取り出しながら反応を行う方法が、それぞれ記載されている。 In addition, a method of performing a dehydration reaction and an isomerization reaction in one step is also known. For example, Patent Document 1 discloses a method of performing dehydration and isomerization in one step using hydrogen chloride or hydrogen bromide in refluxing n-butanol, and Patent Document 5 discloses halogenation in the presence of an inert solvent. A method of carrying out the reaction while removing water out of the system using hydrogen or sulfonic acids. Patent Document 6 discloses water produced using sulfonic acids in the presence of a high-boiling solvent and 2-alkyl-2-cyclopentenone. A method for performing the reaction while taking out from the system is described.
上記脱水反応と異性化反応を別々に行う場合は、特許文献１〜３のように酸で脱水反応が進行し、特許文献４のように金属触媒で異性化反応は進行する。しかし、これらの場合、工程が増えて生産性が低下するうえに、収率も満足いくものではない。
また、特許文献１、５及び６に開示される、脱水反応及び異性化反応を、酸を用いて一段階で行う方法では、使用できる酸は強酸に限られており、反応槽の腐食性が高いため、製造設備としては腐食しない設備を使用する必要があり、また、反応中間体である２−（アルキリデン）シクロアルカノンや生成物である２−アルキル−２−シクロアルケン−１−オンが重合したり、分解したりするので収率の低下が避けられない。さらに、反応終了後のアルカリ処理、水洗処理等により、大量の廃液が副生するという問題がある。
When the dehydration reaction and the isomerization reaction are performed separately, the dehydration reaction proceeds with an acid as in Patent Documents 1 to 3, and the isomerization reaction proceeds with a metal catalyst as in Patent Document 4. However, in these cases, the number of processes increases and productivity decreases, and the yield is not satisfactory.
Moreover, in the method of performing dehydration reaction and isomerization reaction disclosed in Patent Documents 1, 5 and 6 in one step using an acid, the acid that can be used is limited to a strong acid, and the corrosiveness of the reaction tank is low. Since it is expensive, it is necessary to use equipment that does not corrode as production equipment, and 2- (alkylidene) cycloalkanone that is a reaction intermediate and 2-alkyl-2-cycloalkene-1-one that is a product are Since it polymerizes or decomposes, a decrease in yield is inevitable. Furthermore, there is a problem that a large amount of waste liquid is produced as a by-product due to alkali treatment, water washing treatment, and the like after the reaction is completed.
本発明は、２−アルキル−２−シクロアルケン−１−オンを高収率、高純度で得ることができる製造方法を提供することを課題とする。 An object of the present invention is to provide a production method capable of obtaining 2-alkyl-2-cycloalkene-1-one with high yield and high purity.
本発明者は、２−（１−ヒドロキシアルキル）−シクロアルカン−１−オンを、酸と白金族金属触媒の共存下、濃度を経時的に変化させた水素ガス雰囲気下で脱水異性化させることにより、高収率、高純度で目的化合物を合成し得ることを見出した。 The present inventor dehydrates and isomerizes 2- (1-hydroxyalkyl) -cycloalkane-1-one in the presence of an acid and a platinum group metal catalyst in a hydrogen gas atmosphere whose concentration is changed over time. Thus, it was found that the target compound can be synthesized with high yield and high purity.
すなわち、本発明は、下記一般式（１）で表される２−（１−ヒドロキシアルキル）−シクロアルカン−１−オンを原料とし、酸及び白金族金属触媒の共存下で、工程（Ａ）の後に、工程（Ｂ）の工程を含む、下記一般式（２）で表される２−アルキル−２−シクロアルケン−１−オンの製造方法を提供する。
工程（Ａ）：水素ガス濃度５〜４５容量％の雰囲気下で脱水異性化させる工程
工程（Ｂ）：水素ガス濃度１容量％以上、かつ工程（Ａ）における水素濃度よりも２容量％以上低い濃度の雰囲気下で脱水異性化させる工程
That is, the present invention uses 2- (1-hydroxyalkyl) -cycloalkane-1-one represented by the following general formula (1) as a raw material, and in the coexistence of an acid and a platinum group metal catalyst, step (A) After that, a method for producing 2-alkyl-2-cycloalkene-1-one represented by the following general formula (2) including the step (B) is provided.
Step (A): Step of dehydration isomerization in an atmosphere having a hydrogen gas concentration of 5 to 45% by volume Step (B): Hydrogen gas concentration of 1% by volume or more and 2% by volume or more lower than the hydrogen concentration in step (A) Dehydration isomerization process in a concentration atmosphere
（式中、ｎは１又は２の整数、Ｒ1及びＲ2は、それぞれ水素原子又は炭素数１〜８のアルキル基を示すか、又はＲ1とＲ2とに隣接する炭素原子を介してシクロペンタン環又はシクロヘキサン環を形成してもよい。） (In the formula, n is an integer of 1 or 2, R 1 and R 2 each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, or via a carbon atom adjacent to R 1 and R 2. (A cyclopentane ring or a cyclohexane ring may be formed.)
本発明によれば、２−アルキル−２−シクロアルケン−１−オンを高収率、高純度で得ることができる製造方法を提供することができる。 According to the present invention, it is possible to provide a production method capable of obtaining 2-alkyl-2-cycloalkene-1-one with high yield and high purity.
本発明の下記一般式（２）で表される２−アルキル−２−シクロアルケン−１−オン（以下、化合物（２）ともいう）の製造方法は、下記一般式（１）で表される２−（１−ヒドロキシアルキル）−シクロアルカン−１−オン（以下、化合物（１）ともいう）を原料とし、酸及び白金族金属触媒の共存下で、工程（Ａ）の後に、工程（Ｂ）の工程を含むことを特徴とする。
工程（Ａ）：水素ガス濃度５〜４５容量％の雰囲気下で脱水異性化させる工程
工程（Ｂ）：水素ガス濃度１容量％以上、かつ工程（Ａ）における水素濃度よりも２容量％以上低い濃度の雰囲気下で脱水異性化させる工程
The production method of 2-alkyl-2-cycloalkene-1-one (hereinafter also referred to as compound (2)) represented by the following general formula (2) of the present invention is represented by the following general formula (1). 2- (1-hydroxyalkyl) -cycloalkane-1-one (hereinafter also referred to as compound (1)) is used as a raw material, and in the presence of an acid and a platinum group metal catalyst, after step (A), step (B ).
Step (A): Step of dehydration isomerization in an atmosphere having a hydrogen gas concentration of 5 to 45% by volume Step (B): Hydrogen gas concentration of 1% by volume or more and 2% by volume or more lower than the hydrogen concentration in step (A) Dehydration isomerization process in a concentration atmosphere
［化合物（１）及び（２）］
本発明の化合物（２）の製造方法においては、原料として化合物（１）が用いられる。
前記一般式（１）及び（２）において、Ｒ1及びＲ2は、それぞれ独立に水素原子又は炭素数１〜８のアルキル基を示すか、又はＲ1とＲ2とに隣接する炭素原子を介してシクロペンタン環又はシクロヘキサン環を形成してもよい。Ｒ1及びＲ2は、水素原子又は直鎖又は分岐鎖のアルキル基であることが好ましく、水素原子又は直鎖のアルキル基であることがより好ましい。
Ｒ1及びＲ2であるアルキル基としては、例えば、メチル基、エチル基、直鎖又は分岐鎖の各種プロピル基、各種ブチル基、各種ペンチル基、各種ヘキシル基、各種ヘプチル基、各種オクチル基が挙げられる。
ここで、「Ｒ1とＲ2とに隣接する炭素原子を介してシクロペンタン環又はシクロヘキサン環を形成」するとは、Ｒ1が炭素原子を介してＲ2と結合して、又は、Ｒ2が炭素原子を介してＲ1と結合して、５員環又は６員環を形成」することを意味する。なお、炭素原子に結合した水素原子は、例えば炭素数１〜５のアルキル基、アルケニル基等の炭化水素基で置換していてもよい。
[Compounds (1) and (2)]
In the method for producing compound (2) of the present invention, compound (1) is used as a raw material.
In the general formulas (1) and (2), R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, or a carbon atom adjacent to R 1 and R 2. A cyclopentane ring or a cyclohexane ring may be formed. R 1 and R 2 are preferably a hydrogen atom or a linear or branched alkyl group, and more preferably a hydrogen atom or a linear alkyl group.
Examples of the alkyl group as R 1 and R 2 include a methyl group, an ethyl group, various linear or branched propyl groups, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, and various octyl groups. Can be mentioned.
Here, “to form a cyclopentane ring or a cyclohexane ring through a carbon atom adjacent to R 1 and R 2 ” means that R 1 is bonded to R 2 through a carbon atom, or R 2 is It means binding to R 1 through a carbon atom to form a 5-membered or 6-membered ring ”. In addition, the hydrogen atom couple | bonded with the carbon atom may be substituted with hydrocarbon groups, such as a C1-C5 alkyl group and an alkenyl group, for example.
化合物（１）の具体例としては、２−（１−ヒドロキシプロピル）−シクロペンタノン、２−（１−ヒドロキシブチル）−シクロペンタノン、２−（１−ヒドロキシペンチル）−シクロペンタノン、２−（１−ヒドロキシヘキシル）−シクロペンタノン、２−（１−ヒドロキシ−１−メチルブチル）−シクロペンタノン、２−（１−ヒドロキシ−２−メチルブチル）−シクロペンタノン、２−（１−ヒドロキシシクロペンチル）−シクロペンタノン、２−（１−ヒドロキシシクロヘキシル）−シクロペンタノン、２−（１−ヒドロキシプロピル）−シクロヘキサノン、２−（１−ヒドロキシブチル）−シクロヘキサノン、２−（１−ヒドロキシペンチル）−シクロヘキサノン、２−（１−ヒドロキシヘキシル）−シクロヘキサノン、２−（１−ヒドロキシ−１−メチルブチル）−シクロヘキサノン、２−（１−ヒドロキシ−２−メチルブチル）−シクロヘキサノン、２−（１−ヒドロキシシクロペンチル）−シクロヘキサノン、２−（１−ヒドロキシシクロヘキシル）−シクロヘキサノン等が挙げられる。これらの中では、２−（１−ヒドロキシプロピル）−シクロペンタノン、２−（１−ヒドロキシブチル）−シクロペンタノン、２−（１−ヒドロキシペンチル）−シクロペンタノン、２−（１−ヒドロキシヘキシル）−シクロペンタノンが好ましく、２−（１−ヒドロキシペンチル）−シクロペンタノンが特に好ましい。 Specific examples of the compound (1) include 2- (1-hydroxypropyl) -cyclopentanone, 2- (1-hydroxybutyl) -cyclopentanone, 2- (1-hydroxypentyl) -cyclopentanone, 2 -(1-hydroxyhexyl) -cyclopentanone, 2- (1-hydroxy-1-methylbutyl) -cyclopentanone, 2- (1-hydroxy-2-methylbutyl) -cyclopentanone, 2- (1-hydroxy Cyclopentyl) -cyclopentanone, 2- (1-hydroxycyclohexyl) -cyclopentanone, 2- (1-hydroxypropyl) -cyclohexanone, 2- (1-hydroxybutyl) -cyclohexanone, 2- (1-hydroxypentyl) -Cyclohexanone, 2- (1-hydroxyhexyl) -cyclohexanone, 2- (1 Hydroxy-1-methylbutyl) - cyclohexanone, 2- (1-hydroxy-2-methylbutyl) - cyclohexanone, 2- (1-hydroxycyclopentyl) - cyclohexanone, 2- (1-hydroxycyclohexyl) - cyclohexanone. Among these, 2- (1-hydroxypropyl) -cyclopentanone, 2- (1-hydroxybutyl) -cyclopentanone, 2- (1-hydroxypentyl) -cyclopentanone, 2- (1-hydroxy Hexyl) -cyclopentanone is preferred, and 2- (1-hydroxypentyl) -cyclopentanone is particularly preferred.
化合物（２）の具体例としては、２−プロピル−２−シクロペンテン−１−オン、２−ブチル−２−シクロペンテン−１−オン、２−ペンチル−２−シクロペンテン−１−オン、２−ヘキシル−２−シクロペンテン−１−オン、２−（１−メチルブチル）−２−シクロペンテン−１−オン、２−（２−メチルブチル）−２−シクロペンテン−１−オン、２−シクロペンチル−２−シクロペンテン−１−オン、２−シクロヘキシル−２−シクロペンテン−１−オン、２−プロピル−２−シクロヘキセン−１−オン、２−ブチル−２−シクロヘキセン−１−オン、２−ペンチル−２−シクロヘキセン−１−オン、２−ヘキシル−２−シクロヘキセン−１−オン、２−（１−メチルブチル）−２−シクロヘキセン−１−オン、２−（２−メチルブチル）−２−シクロヘキセン−１−オン、２−シクロペンチル−２−シクロヘキセン−１−オン、２−シクロヘキシル−２−シクロヘキセン−１−オン等が挙げられる。これらの中では、２−プロピル−２−シクロペンテン−１−オン、２−ブチル−２−シクロペンテン−１−オン、２−ペンチル−２−シクロペンテン−１−オン、２−ヘキシル−２−シクロペンテン−１−オンが好ましく、２−ペンチル−２−シクロペンテン−１−オンが特に好ましい。 Specific examples of the compound (2) include 2-propyl-2-cyclopenten-1-one, 2-butyl-2-cyclopenten-1-one, 2-pentyl-2-cyclopenten-1-one, 2-hexyl- 2-cyclopenten-1-one, 2- (1-methylbutyl) -2-cyclopenten-1-one, 2- (2-methylbutyl) -2-cyclopenten-1-one, 2-cyclopentyl-2-cyclopentene-1- ON, 2-cyclohexyl-2-cyclopenten-1-one, 2-propyl-2-cyclohexen-1-one, 2-butyl-2-cyclohexen-1-one, 2-pentyl-2-cyclohexen-1-one, 2-hexyl-2-cyclohexen-1-one, 2- (1-methylbutyl) -2-cyclohexen-1-one, 2- (2-methylbutyrate) ) -2-cyclohexen-1-one, 2-cyclopentyl-2-cyclohexen-1-one, 2-cyclohexyl-2-cyclohexen-1-one, and the like. Among these, 2-propyl-2-cyclopenten-1-one, 2-butyl-2-cyclopenten-1-one, 2-pentyl-2-cyclopenten-1-one, 2-hexyl-2-cyclopentene-1 -One is preferred, and 2-pentyl-2-cyclopenten-1-one is particularly preferred.
［化合物（１）の製法］
化合物（１）は、公知の方法により製造することができる。例えば、炭素数５又は６のシクロアルカノンと、下記一般式（３）で表されるアルデヒド又はケトンを反応させることにより得ることができる。
本発明では、このような方法で得られる化合物（１）を精製せずに用いることもできるが、触媒の活性が低下する場合は蒸留等により精製して使用してもよい。
[Production Method of Compound (1)]
Compound (1) can be produced by a known method. For example, it can be obtained by reacting a cycloalkanone having 5 or 6 carbon atoms with an aldehyde or ketone represented by the following general formula (3).
In the present invention, the compound (1) obtained by such a method can be used without purification, but may be used after purification by distillation or the like when the activity of the catalyst decreases.
［化合物（２）の製法］
本発明において化合物（２）は、酸及び白金族金属触媒の共存下で、濃度を経時的に変化させた水素ガス雰囲気下に化合物（１）を脱水異性化反応させることにより製造される。より具体的には、化合物（２）は、酸及び白金族金属触媒の共存下で、工程（Ａ）水素ガス濃度５〜４５容量％の雰囲気下で脱水異性化させる工程を行った後、工程（Ｂ）水素ガス濃度１容量％以上、かつ工程（Ａ）における水素濃度よりも２容量％以上低い濃度の雰囲気下で脱水異性化させる工程を行うことにより製造される。
[Production Method of Compound (2)]
In the present invention, the compound (2) is produced by subjecting the compound (1) to a dehydration isomerization reaction in a hydrogen gas atmosphere whose concentration is changed with time in the presence of an acid and a platinum group metal catalyst. More specifically, the compound (2) is obtained by performing step (A) dehydration isomerization in an atmosphere having a hydrogen gas concentration of 5 to 45% by volume in the presence of an acid and a platinum group metal catalyst, (B) It is produced by performing a dehydration isomerization step in an atmosphere having a hydrogen gas concentration of 1% by volume or more and 2% by volume or less lower than the hydrogen concentration in step (A).
＜酸＞
本発明に用いられる酸としては、無機酸、有機酸、及び固体酸等を用いることができる。
（無機酸及び有機酸）
無機酸及び有機酸としては、一般的な酸を用いることができる。具体的には、塩酸、硫酸、リン酸、オルトリン酸、メタリン酸、ピロリン酸、トリポリリン酸等の縮合リン酸等の無機酸、酢酸、シュウ酸、クエン酸、マレイン酸、フマル酸、リンゴ酸等の有機酸が挙げられる。なかでも、沸点の点から、リン酸、ピロリン酸、トリポリリン酸等の縮合リン酸、シュウ酸、クエン酸、マレイン酸、フマル酸、及びリンゴ酸等の有機酸がより好ましく、リン酸、シュウ酸が特に好ましい。これらの酸は１種単独で、又は２種以上を組み合わせて用いることができる。
<Acid>
As an acid used in the present invention, an inorganic acid, an organic acid, a solid acid, or the like can be used.
(Inorganic and organic acids)
As the inorganic acid and organic acid, general acids can be used. Specifically, inorganic acids such as condensed phosphoric acid such as hydrochloric acid, sulfuric acid, phosphoric acid, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, acetic acid, oxalic acid, citric acid, maleic acid, fumaric acid, malic acid, etc. The organic acid is mentioned. Among these, from the viewpoint of boiling point, condensed phosphoric acid such as phosphoric acid, pyrophosphoric acid, and tripolyphosphoric acid, and organic acids such as oxalic acid, citric acid, maleic acid, fumaric acid, and malic acid are more preferable, and phosphoric acid and oxalic acid. Is particularly preferred. These acids can be used alone or in combination of two or more.
（固体酸）
固体酸としては、公知の固体酸を用いることができる。具体的には、活性アルミナ、硫酸ジルコニア、金属リン酸塩、トリポリリン酸二水素アルミニウム、酸化チタン等の無機金属固体や、カチオン交換樹脂、シリカ−チタニア複合酸化物、シリカ−酸化カルシウム複合酸化物、シリカ−マグネシア複合酸化物、ゼオライト等が挙げられる。
固体酸は、アンモニア昇温脱離（ＴＰＤ；Temperature Programmed Desorption）法において、１００〜２５０℃の温度範囲でアンモニア（ＮＨ3）の脱離を起こす酸点の量（ｍｍｏｌ／ｇ）が、２５０℃より高い温度でＮＨ3の脱離を起こす酸点の量（ｍｍｏｌ／ｇ）より多いものがより好ましい。１００〜２５０℃の範囲でＮＨ3の脱離を起こす酸点の量は、０．３ｍｍｏｌ／ｇ以上であり、かつ２５０℃より高い温度でＮＨ3の脱離を起こす酸点の量は、０．３ｍｍｏｌ／ｇ未満であることがより好ましい。
(Solid acid)
A known solid acid can be used as the solid acid. Specifically, an inorganic metal solid such as activated alumina, zirconia sulfate, metal phosphate, aluminum dihydrogen phosphate, titanium oxide, cation exchange resin, silica-titania composite oxide, silica-calcium oxide composite oxide, Examples thereof include silica-magnesia composite oxide and zeolite.
The solid acid has an acid point amount (mmol / g) that causes desorption of ammonia (NH 3 ) in a temperature range of 100 to 250 ° C. in a temperature programmed desorption (TPD) method at 250 ° C. More than the amount of acid sites (mmol / g) causing NH 3 elimination at a higher temperature is more preferable. The amount of acid sites causing NH 3 elimination in the range of 100 to 250 ° C. is 0.3 mmol / g or more, and the amount of acid sites causing NH 3 elimination at temperatures higher than 250 ° C. is 0 More preferably, it is less than 3 mmol / g.
上記の酸点の量は、触媒学会参照触媒であるゼオライト；ＪＲＣ−Ｚ５−２５Ｈのｈｉｇｈピーク（観測される２種のピークのうち、高温側のピーク）を０．９９ｍｍｏｌ／ｇとしてこれに対する相対的な量として測定する。ピークの検出は、質量スペクトルにおけるアンモニアのｍ／ｅ＝１６のフラグメントでアンモニアを定量することにより行う。
ＴＰＤ（アンモニア昇温脱離）の測定法としては、一般的に行われる測定法を用いることができる。例えば、以下のような条件で前処理、ＮＨ3吸着処理、真空処理を順に行った後、ＴＰＤ測定を行う。
前処理：ヘリウムガス中２００℃まで２０分で昇温、１時間保持
ＮＨ3吸着処理：５０℃、２．７ｋＰａで１０分間ＮＨ3を吸着
真空処理：５０℃、４時間処理
ＴＰＤ測定：ヘリウムガスを５０ｍｌ／ｍｉｎで流通、昇温速度５℃／ｍｉｎで６００℃まで昇温
The amount of the above-mentioned acid sites is relative to the zeolite which is a reference catalyst of the Catalytic Society; the high peak of JRC-Z5-25H (the peak on the high temperature side of the two observed peaks) is 0.99 mmol / g Measure as a typical quantity. Peak detection is performed by quantifying ammonia with a m / e = 16 fragment of ammonia in the mass spectrum.
As a measuring method of TPD (ammonia temperature-programmed desorption), a generally performed measuring method can be used. For example, after pre-processing, NH 3 adsorption processing, and vacuum processing are sequentially performed under the following conditions, TPD measurement is performed.
Pretreatment: Raise in helium gas to 200 ° C in 20 minutes, hold for 1 hour NH 3 adsorption treatment: Adsorb NH 3 at 50 ° C, 2.7 kPa for 10 minutes Vacuum treatment: treatment at 50 ° C for 4 hours TPD measurement: Helium gas Circulated at 50 ml / min, heated to 600 ° C at a heating rate of 5 ° C / min
このような酸点の分布をもつ固体酸としては、例えば、下記構造（Ａ）、構造（Ｂ）及び金属原子（Ｃ）の少なくとも１つを有するものが好ましく挙げられ、なかでも構造（Ａ）と金属原子（Ｃ）、構造（Ｂ）と金属原子（Ｃ）、及び構造（Ａ）と構造（Ｂ）と金属原子（Ｃ）を含む固体酸が好ましい。
・構造（Ａ）：無機リン酸が有するＯＨ基の少なくとも一つから水素原子が除かれた構造
・構造（Ｂ）：下記一般式（４）又は（５）で表される有機リン酸が有するＯＨ基の少なくとも一つから水素原子が除かれた構造
・金属原子（Ｃ）：アルミニウム、ガリウム及び鉄から選ばれる１種以上の金属原子
Preferred examples of the solid acid having such a distribution of acid points include those having at least one of the following structure (A), structure (B), and metal atom (C), among which structure (A) And a solid acid containing a metal atom (C), a structure (B) and a metal atom (C), and a structure (A), a structure (B) and a metal atom (C) are preferable.
Structure (A): Structure in which a hydrogen atom is removed from at least one OH group of inorganic phosphoric acidStructure (B): Organophosphoric acid represented by the following general formula (4) or (5) Structure in which hydrogen atom is removed from at least one of OH groups Metal atom (C): One or more metal atoms selected from aluminum, gallium and iron
（式中、Ｒ4及びＲ5は、それぞれＲ6、ＯＲ6、ＯＨ、Ｈから選ばれ、Ｒ4及びＲ5の少なくとも一方は、Ｒ6又はＯＲ6である。ただし、Ｒ6は炭素数１〜２２の有機基であり、炭素数１〜１５の有機基が好ましく、炭素数１〜６の有機基がより好ましい。） (Wherein R 4 and R 5 are each selected from R 6 , OR 6 , OH and H, and at least one of R 4 and R 5 is R 6 or OR 6 , where R 6 is the number of carbon atoms. An organic group having 1 to 22 carbon atoms, preferably an organic group having 1 to 15 carbon atoms, and more preferably an organic group having 1 to 6 carbon atoms.)
構造（Ａ）としては、オルトリン酸、メタリン酸、ピロリン酸等の縮合リン酸等が挙げられる。これらの中では、性能の点から、オルトリン酸から誘導されるが構造（Ａ）好ましい。
また構造（Ｂ）において、一般式（４）又は（５）で表される有機リン酸としては、ホスホン酸、ホスホン酸モノエステル、ホスフィン酸、リン酸モノエステル、リン酸ジエステル、亜リン酸モノエステル、亜リン酸ジエステル等が挙げられ、これらの混合物でもよい。これらの中では、ホスホン酸から誘導される構造（Ｂ）が好ましい。
また、有機基Ｒ6としては、好ましくは炭素数１〜１５、より好ましくは炭素数１〜８の有機基が好ましく、メチル基、エチル基、プロピル基、イソプロピル基、各種ブチル基、各種ペンチル基、各種ヘキシル基、各種オクチル基等のアルキル基、フェニル基、３−メチルフェニル基等のアリール基等が挙げられる。
Examples of the structure (A) include condensed phosphoric acid such as orthophosphoric acid, metaphosphoric acid, and pyrophosphoric acid. In these, although derived from orthophosphoric acid from the point of performance, structure (A) is preferable.
In the structure (B), examples of the organic phosphoric acid represented by the general formula (4) or (5) include phosphonic acid, phosphonic monoester, phosphinic acid, phosphoric monoester, phosphoric diester, and phosphorous monoester. Examples thereof include esters and phosphorous acid diesters, and a mixture thereof may be used. Among these, the structure (B) derived from phosphonic acid is preferable.
The organic group R 6 is preferably an organic group having 1 to 15 carbon atoms, more preferably 1 to 8 carbon atoms, and is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, various butyl groups, or various pentyl groups. And alkyl groups such as various hexyl groups and various octyl groups, and aryl groups such as phenyl group and 3-methylphenyl group.
金属原子（Ｃ）としては、性能及び／又はコストの点から、アルミニウムが好ましい。なお、選択性その他性能を改良する目的で、アルミニウム、ガリウム、鉄以外の金属原子を少量有してもよい。また触媒中に含まれる金属原子（Ｃ）の全てが、必ずしも、構造（Ａ）又は構造（Ｂ）と結合している必要はなく、金属原子（Ｃ）の一部分が金属酸化物又は金属水酸化物等の形で存在していてもよい。 As the metal atom (C), aluminum is preferable from the viewpoint of performance and / or cost. For the purpose of improving selectivity and other performance, a small amount of metal atoms other than aluminum, gallium, and iron may be included. Further, not all of the metal atoms (C) contained in the catalyst are necessarily bonded to the structure (A) or the structure (B), and a part of the metal atoms (C) is a metal oxide or metal hydroxide. It may exist in the form of a thing or the like.
固体酸の調製法として、沈殿法や金属酸化物又は水酸化物に無機リン酸及び有機リン酸を含浸する方法、無機リン酸アルミニウムゲル中の無機リン酸基を有機リン酸基へ置換する方法等が用いられ、これらの中では沈殿法が好ましい。
また、固体酸を調製する際に、高表面積の担体を共存させ、担持触媒を得ることも可能である。担体として、シリカ、アルミナ、シリカアルミナ、チタニア、ジルコニア、ケイソウ土、活性炭等を用いることができる。担体を過剰に用いると、活性成分の含有量が低下し、活性を低下させるため、触媒中の担体の占める割合は、９０重量％以下が好ましい。
固体酸の形状は、粉末でも成型したものでもよい。また、固体酸は、全て同一組成であってもよく、異なる組成の固体酸を組み合わせて用いてもよい。
Preparation method of solid acid: precipitation method, method of impregnating metal oxide or hydroxide with inorganic phosphoric acid and organic phosphoric acid, method of replacing inorganic phosphate group in inorganic aluminum phosphate gel with organic phosphate group Among these, the precipitation method is preferable.
Moreover, when preparing a solid acid, it is also possible to obtain a supported catalyst by coexisting a high surface area carrier. As the carrier, silica, alumina, silica alumina, titania, zirconia, diatomaceous earth, activated carbon, or the like can be used. If the carrier is used in excess, the content of the active ingredient is lowered and the activity is lowered. Therefore, the proportion of the carrier in the catalyst is preferably 90% by weight or less.
The shape of the solid acid may be a powder or a molded one. Moreover, all the solid acids may have the same composition, or a combination of solid acids having different compositions may be used.
上記の無機酸、有機酸、及び固体酸は、それぞれ単独で又は２種以上を組み合わせて用いることができる。固体酸のみを用いる場合は、中和工程を省略することもできる。
酸の使用量は、反応性の観点から、原料に対し０．０００１質量％以上が好ましい。一方、生成する二重結合を含む化合物間の重合を抑え、収率を向上させるという観点から、酸の使用量は２５質量％以下が好ましい。上記観点から、酸の使用量は、０．００１〜１２質量％がより好ましく、０．０１〜６質量％が特に好ましい。
Said inorganic acid, organic acid, and solid acid can be used individually or in combination of 2 types or more, respectively. When using only a solid acid, a neutralization process can also be skipped.
The amount of the acid used is preferably 0.0001% by mass or more based on the raw material from the viewpoint of reactivity. On the other hand, the amount of acid used is preferably 25% by mass or less from the viewpoint of suppressing the polymerization between the compounds containing a double bond to be generated and improving the yield. From the above viewpoint, the amount of the acid used is more preferably 0.001 to 12% by mass, and particularly preferably 0.01 to 6% by mass.
＜白金族金属触媒＞
本発明に用いられる白金族金属触媒は、周期律表第５〜６周期の第８〜１０族元素に含まれる、オスミウム（Ｏｓ）、ルテニウム（Ｒｕ）、イリジウム（Ｉｒ）、ロジウム（Ｒｈ）、白金（Ｐｔ）及びパラジウム（Ｐｄ）からなる群から選ばれる１種以上の金属成分を主成分として含む触媒である。これらの金属成分の中では、触媒活性等の観点から、Ｐｔ及びＰｄが好ましく、Ｐｄがより好ましい。またこれらの金属成分は、１種単独で又は２種以上を組み合わせて用いることができる。ここで、「主成分として含む」とは、触媒金属成分中に、当該成分を好ましくは５０モル％以上、より好ましくは７０モル％以上、より好ましくは９０モル％以上、更に好ましくは９５モル％以上含むことを意味する。
これらの白金族金属触媒は、他の金属成分又は副次量の助触媒を含有していてもよい。このような他の金属成分の例としては、例えば、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ等の周期律表第４周期の第４〜１１族元素や、Ｗ、Ａｇ及びＡｕ等が挙げられる。
<Platinum group metal catalyst>
The platinum group metal catalyst used in the present invention includes osmium (Os), ruthenium (Ru), iridium (Ir), rhodium (Rh), which are included in Group 8 to 10 elements of Periodic Tables 5-6. A catalyst containing one or more metal components selected from the group consisting of platinum (Pt) and palladium (Pd) as a main component. Among these metal components, Pt and Pd are preferable and Pd is more preferable from the viewpoint of catalytic activity and the like. Moreover, these metal components can be used individually by 1 type or in combination of 2 or more types. Here, “including as a main component” means that the component is preferably 50 mol% or more, more preferably 70 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% in the catalyst metal component. It means including the above.
These platinum group metal catalysts may contain other metal components or secondary amounts of promoters. Examples of such other metal components include, for example, Group 4 to 11 elements of the fourth period of the periodic table such as Ti, V, Cr, Mn, Fe, Co, Ni, Cu, W, Ag, and the like. Au etc. are mentioned.
触媒は、担持型、ラネー型、可溶型、粉末状、顆粒状等の形態に適宜調製して使用することができる。
担持型触媒は、触媒の耐久性等の物理的特性を改善するために金属成分を担体に担持した触媒である。担持型触媒の調製は、沈殿法、イオン交換法、蒸発乾固法、噴霧乾燥法、混練法等の公知の方法により行うことができる。担体としては、炭素（活性炭）、アルミナ、シリカ、シリカ−アルミナ、硫酸バリウム及び炭酸カルシウム等が挙げられる。これらの中では、炭素（活性炭）、シリカ、アルミナ、シリカ−アルミナが好ましい。
触媒としてパラジウム触媒を用いる場合の具体例としては、パラジウムカーボン、パラジウム担持アルミナ、パラジウム担持硫酸バリウム、パラジウム担持炭酸カルシウム等が挙げられる。これらの中では、反応性が高く、反応後にパラジウム触媒を容易に回収可能なパラジウムカーボン、パラジウム担持アルミナが好ましく、入手性や取り扱いの簡便さ、反応性等の観点から、パラジウムカーボンが特に好ましい。
担持型触媒における金属成分の担持量は、触媒活性の点から、担体と担持された金属成分との合計量に基づき、通常０．１〜７０質量％程度が好ましい。
ラネー型触媒は多孔質のスポンジ状金属触媒であり、例えば、久保松照夫、小松信一郎著、「ラネー触媒」、共立出版（１９７１））等により調製することができる。
可溶型触媒を用いる場合は、例えば、硝酸、塩酸などの無機酸などの金属塩水溶液、又は各種金属塩の混合水溶液を反応系に滴下すればよい。
なお、上記の触媒として市販品を使用することもできる。
The catalyst can be appropriately prepared and used in a supported type, Raney type, soluble type, powdered form, granular form or the like.
A supported catalyst is a catalyst in which a metal component is supported on a carrier in order to improve physical properties such as durability of the catalyst. The supported catalyst can be prepared by a known method such as a precipitation method, an ion exchange method, an evaporation to dryness method, a spray drying method, or a kneading method. Examples of the carrier include carbon (activated carbon), alumina, silica, silica-alumina, barium sulfate and calcium carbonate. Among these, carbon (activated carbon), silica, alumina, and silica-alumina are preferable.
Specific examples of using a palladium catalyst as the catalyst include palladium carbon, palladium-supported alumina, palladium-supported barium sulfate, palladium-supported calcium carbonate, and the like. Among these, palladium carbon and palladium-supported alumina that are highly reactive and can easily recover the palladium catalyst after the reaction are preferable, and palladium carbon is particularly preferable from the viewpoints of availability, ease of handling, reactivity, and the like.
The supported amount of the metal component in the supported catalyst is usually preferably about 0.1 to 70% by mass based on the total amount of the carrier and the supported metal component from the viewpoint of catalytic activity.
The Raney-type catalyst is a porous sponge-like metal catalyst and can be prepared, for example, by Teruo Kubomatsu and Shinichiro Komatsu, “Raney Catalyst”, Kyoritsu Shuppan (1971)).
When a soluble catalyst is used, for example, an aqueous metal salt solution such as an inorganic acid such as nitric acid or hydrochloric acid, or a mixed aqueous solution of various metal salts may be dropped into the reaction system.
In addition, a commercial item can also be used as said catalyst.
白金族金属触媒の使用量は、反応形式により適宜最適化することができる。
回分式の場合は、反応性及び経済性の観点から、原料である化合物（１）に対して、金属量として０．０００２〜３質量％が好ましく、０．００２〜２質量％がより好ましく、０．００５〜１質量％がさらに好ましい。
酸と白金族金属触媒は、別々の形態で用いることもでき、また一つの形態を有する触媒として使用することもできる。例えば、酸性の担体に白金族金属を担持する形態とすれば、酸を別途添加する必要がない。
酸及び白金族金属触媒を用いる場合は、懸濁床でも固定床でもよい。
担体に担持させた酸、又は固体酸を用いた固定床反応の場合には、触媒等と反応終了物との分離工程が要らないことから、大量生産する際には有効である。
懸濁床反応でも固体触媒を使用すれば、濾過等により触媒等と反応液とを容易に分離することができ、触媒をリサイクルすることも可能である。また、反応形式は、液相でも気相でも、また回分式でも連続式でも行うことができる。
The amount of platinum group metal catalyst used can be optimized as appropriate depending on the reaction mode.
In the case of a batch system, from the viewpoint of reactivity and economy, the amount of metal is preferably 0.0002 to 3% by mass, more preferably 0.002 to 2% by mass with respect to the compound (1) as a raw material. 0.005-1 mass% is still more preferable.
The acid and the platinum group metal catalyst can be used in separate forms, or can be used as a catalyst having one form. For example, when the platinum group metal is supported on an acidic carrier, it is not necessary to add an acid separately.
When an acid and a platinum group metal catalyst are used, a suspended bed or a fixed bed may be used.
In the case of a fixed bed reaction using an acid supported on a support or a solid acid, a separation step of a catalyst or the like and a reaction end product is not required, which is effective for mass production.
If a solid catalyst is used in the suspension bed reaction, the catalyst and the reaction solution can be easily separated by filtration or the like, and the catalyst can be recycled. The reaction can be carried out in a liquid phase or a gas phase, or a batch type or a continuous type.
＜脱水異性化の反応条件＞
（水素ガス濃度）
本発明における脱水異性化において、反応前半の工程（Ａ）での水素ガス濃度は、白金族触媒を活性化する観点から５〜４５容量％であり、５〜４０容量％が好ましい。また、場合により、反応前半の工程（Ａ）での水素ガス濃度は、１５〜４５容量％が好ましく、１５〜４０容量％がより好ましい。
また、反応後半の工程（Ｂ）での水素ガス濃度は、後述する化合物（６）の副生を抑える観点から、１容量％以上、かつ工程（Ａ）における水素濃度よりも２容量％以上低い濃度あり、１．５容量％以上、かつ工程（Ａ）における水素濃度よりも２容量％以上低い濃度が好ましく、２容量％以上、かつ工程（Ａ）における水素濃度よりも３容量％以上低い濃度が特に好ましい。
また、場合により、反応後半の工程（Ｂ）での水素ガス濃度は、５容量％以上、かつ工程（Ａ）における水素濃度よりも２容量％以上低い濃度が好ましく、５容量％以上、かつ工程（Ａ）における水素濃度よりも５容量％以上低い濃度がより好ましく、５容量％以上、かつ工程（Ａ）における水素濃度よりも８容量％以上低い濃度が更に好ましい。
また、水素ガス濃度は、工程（Ａ）又は工程（Ｂ）の工程中で一定でもよく、上記の濃度範囲内にあれば、変動させてもよい。
<Reaction conditions for dehydration isomerization>
(Hydrogen gas concentration)
In the dehydration isomerization in the present invention, the hydrogen gas concentration in the first half of the reaction (A) is 5 to 45% by volume, preferably 5 to 40% by volume from the viewpoint of activating the platinum group catalyst. In some cases, the hydrogen gas concentration in the first half of the reaction (A) is preferably 15 to 45% by volume, more preferably 15 to 40% by volume.
Further, the hydrogen gas concentration in the second half of the reaction (B) is 1% by volume or more and 2% by volume or more lower than the hydrogen concentration in the step (A) from the viewpoint of suppressing by-product formation of the compound (6) described later. Concentration, 1.5% by volume or more, preferably 2% or more by volume lower than the hydrogen concentration in step (A), 2% by volume or more and 3% by volume or more lower than the hydrogen concentration in step (A) Is particularly preferred.
In some cases, the hydrogen gas concentration in step (B) in the latter half of the reaction is preferably 5% by volume or more and preferably 2% by volume or more lower than the hydrogen concentration in step (A), and 5% by volume or more. A concentration that is 5% by volume or more lower than the hydrogen concentration in (A) is more preferable, and a concentration that is 5% by volume or more and 8% by volume or more lower than the hydrogen concentration in step (A) is more preferable.
Further, the hydrogen gas concentration may be constant during the step (A) or the step (B), and may be varied as long as it is within the above concentration range.
水素ガスは不活性ガスとの混合ガスとして用いることが好ましく、脱水異性化は、当該混合ガス雰囲気下又は流通下で行うことが好ましい。不活性ガスとしては、窒素ガス、アルゴンガス、ヘリウムガス等が好ましく挙げられ、なかでも窒素ガスが好ましい。 Hydrogen gas is preferably used as a mixed gas with an inert gas, and dehydration isomerization is preferably performed in the mixed gas atmosphere or under circulation. Preferred examples of the inert gas include nitrogen gas, argon gas, helium gas, and nitrogen gas is particularly preferable.
本発明において、脱水異性化における中間体及び／又は生成物の一部は、水素ガスにより二重結合が還元され、下記一般式（６）で表される２−アルキルシクロアルカン−１−オン（以下、化合物（６）ともいう）が生成する。 In the present invention, some of the intermediates and / or products in the dehydration isomerization are reduced in double bonds by hydrogen gas, and 2-alkylcycloalkane-1-one represented by the following general formula (6) ( Hereinafter, compound (6) is also formed.
なお、化合物（６）は、例えば特開平９−１０４６８１号公報に記載されているように、過酢酸等を酸化剤として用い、バイヤービリガー（Ｂａｅｙｅｒ−Ｖｉｌｌｉｇｅｒ）酸化反応（ケトンと過カルボン酸を反応させて、ケトンのカルボニル基の隣りに酸素原子が挿入されたカルボン酸エステルを得る酸化反応）を行わせることにより、香料素材として有用な、下記一般式（７）で表される５−アルキル−５−アルカノリドを製造することができる。 As described in JP-A-9-104681, for example, compound (6) uses a peracetic acid or the like as an oxidizing agent, and a Bayer-Villiger oxidation reaction (reacts a ketone with a percarboxylic acid). 5-alkyl- represented by the following general formula (7), which is useful as a perfume material, by carrying out an oxidation reaction to obtain a carboxylic acid ester having an oxygen atom inserted next to the carbonyl group of the ketone. 5-Alkanolides can be produced.
（反応条件）
本発明における脱水異性化の反応温度は、７０〜３００℃が好ましい。反応を短時間で終了させ、化合物（２）の重合及び分解を防いで収率を高めるという観点から、９０〜２００℃がより好ましく、１００〜１７０℃がさらに好ましく、１３０〜１６０℃が特に好ましい。
脱水異性化は、常圧でも進行するが、減圧下で反応させることにより、生成する水を効率的に系外へ留去させ、原料及び反応生成物を留出させないで効率的に反応させることができる。反応圧力としては、反応温度に応じ、２０〜２００ｋＰａの範囲とすることが好ましく、５０〜１５０ｋＰａの範囲とすることがより好ましい。本発明の方法においては、生成する水を留去しながら反応を行うことが好ましい。
脱水異性化の反応時間については化合物（２）を高収率、高純度で得る観点から、工程（Ａ）の反応時間を工程（Ａ）及び（Ｂ）の合計反応時間の５％〜５０％とすることが好ましく、１０％〜４０％とすることがより好ましく、１０％〜３５％とすることが更に好ましい。
(Reaction conditions)
The reaction temperature of dehydration isomerization in the present invention is preferably 70 to 300 ° C. 90 to 200 ° C is more preferable, 100 to 170 ° C is more preferable, and 130 to 160 ° C is particularly preferable, from the viewpoint of completing the reaction in a short time and preventing the polymerization and decomposition of the compound (2) to increase the yield. .
Dehydration isomerization proceeds even at normal pressure, but by reacting under reduced pressure, the water produced is efficiently distilled out of the system and reacted efficiently without distilling the raw materials and reaction products. Can do. The reaction pressure is preferably in the range of 20 to 200 kPa, more preferably in the range of 50 to 150 kPa, depending on the reaction temperature. In the method of the present invention, it is preferable to carry out the reaction while distilling off the produced water.
Regarding the reaction time of dehydration isomerization, from the viewpoint of obtaining compound (2) in high yield and high purity, the reaction time of step (A) is 5% to 50% of the total reaction time of steps (A) and (B). It is preferable to be 10% to 40%, more preferably 10% to 35%.
＜溶媒＞
本発明は、溶媒の存在下でも不存在下でも行うことができる。溶媒を使用しない場合は生産性、経済性の観点から有利である。溶媒としては、特に制限されないが、不活性有機溶媒、例えば、メタノール、エタノール、プロパノール、イソプロパノール等のアルコール類、メチルエチルケトン、メチルイソプロピルケトン、メチルプロピルケトン等のケトン類、イソプロピルエーテル、ｎ−ブチルエーテル、１，４−ジオキサン、イソアミルエーテル、ｎ−ヘキシルエーテル等のエーテル類、ギ酸ｎ−メチル、ギ酸ｎ−プロピル、ギ酸ｎ−ブチル、酢酸メチル、酢酸イソプロピル、酢酸ｎ-ブチル等のエステル類、ｎ−へキサン、ｎ−オクタン、ｎ−デカン、リグロイン、シクロヘキサン、ベンゼン、トルエン、キシレン、エチルベンゼン等の炭化水素類等が挙げられる。これらの溶媒は、１種単独で又は２種以上を組み合わせて用いることができる。
溶媒の使用量は、原料の化合物（１）に対して、０．１〜５質量倍とすることが好ましく、０．３〜２質量倍とすることがより好ましい。
<Solvent>
The present invention can be carried out in the presence or absence of a solvent. When no solvent is used, it is advantageous from the viewpoint of productivity and economy. The solvent is not particularly limited, but is an inert organic solvent, for example, alcohols such as methanol, ethanol, propanol, and isopropanol, ketones such as methyl ethyl ketone, methyl isopropyl ketone, and methyl propyl ketone, isopropyl ether, n-butyl ether, 1 , 4-dioxane, isoamyl ether, ethers such as n-hexyl ether, esters such as n-methyl formate, n-propyl formate, n-butyl formate, methyl acetate, isopropyl acetate, n-butyl acetate, n-to Examples thereof include hydrocarbons such as xane, n-octane, n-decane, ligroin, cyclohexane, benzene, toluene, xylene, and ethylbenzene. These solvents can be used alone or in combination of two or more.
The amount of the solvent used is preferably 0.1 to 5 times by mass and more preferably 0.3 to 2 times by mass relative to the raw material compound (1).
本発明の化合物（２）の製造方法によれば、反応中間体である２−（アルキリデン）シクロアルカノン、生成物である２−アルキル−２−シクロアルケン−１−オンの重合を防ぐことが可能となり、化合物（２）を高収率、高純度で得ることができる。また、腐食性、毒性の低い酸及び白金族金属触媒を用いて目的化合物を製造すること、酸及び白金族金属触媒の再利用、及び溶媒を使用しなくても目的化合物を製造することが可能である。 According to the production method of the compound (2) of the present invention, it is possible to prevent polymerization of 2- (alkylidene) cycloalkanone which is a reaction intermediate and 2-alkyl-2-cycloalkene-1-one which is a product. Thus, the compound (2) can be obtained with high yield and high purity. In addition, it is possible to produce the target compound using a corrosive, low-toxic acid and a platinum group metal catalyst, reuse of the acid and the platinum group metal catalyst, and without using a solvent. It is.
以下の例において、「％」は特記しない限り「質量％」である。また、反応圧力は、すべて１０１ｋＰａ（大気圧）である。
生成物の定量は、ガスクロマトグラフィー（ＧＣ）分析（Ａｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｙ社製、６８９０Ｎ、カラム：ＤＢ−１（３０ｍ×０．２５ｍｍ×０．２５μｍ）、オーブン：１００℃→５℃／ｍｉｎ．→２１０℃→２０℃／ｍｉｎ．→２８０℃（４．５ｍｉｎ．ｈｏｌｄ）（計３０ｍｉｎ．）、キャリア：Ｈｅ、流量：１．６ｍＬ／ｍｉｎ．、注入口：２００℃、検出器（ＦＩＤ）：２８０℃、注入量:１μＬ，スプリット：１００:１）による内部標準法（内部標準：ウンデカン（ナカライテスク株式会社製、純度９９％））によって行った。
In the following examples, “%” is “% by mass” unless otherwise specified. The reaction pressure is all 101 kPa (atmospheric pressure).
The product was quantified by gas chromatography (GC) analysis (manufactured by Agilent Technology, 6890N, column: DB-1 (30 m × 0.25 mm × 0.25 μm), oven: 100 ° C. → 5 ° C./min.→210 ° C → 20 ° C / min. → 280 ° C (4.5 min.hold) (total 30 min.), Carrier: He, flow rate: 1.6 mL / min., Inlet: 200 ° C, detector (FID): 280 ° C , Injection amount: 1 μL, split: 100: 1) (internal standard: undecane (manufactured by Nacalai Tesque, Inc., purity 99%)).
合成例１（２−（１−ヒドロキシペンチル）−シクロペンタン−１−オンの合成）
滴下槽を備えた６ｍ3の反応槽に、シクロペンタノン２２４１ｋｇ（２６．６ｋｍｏｌ）、水１００７ｋｇ、４８％ＮａＯＨ１１ｋｇを仕込み、撹拌しながら１５℃に冷却した後、同温度でバレルアルデヒド９８５ｋｇ（１１．４ｋｍｏｌ）を５時間かけて滴下した後、１時間撹拌した。反応終了後、中和し、過剰のシクロペンタノンを蒸留回収した。有機層の反応終了品１８６８ｋｇ中には２−（１−ヒドロキシペンチル）−シクロペンタン−１−オン １７０６ｋｇが含まれていた。
Synthesis Example 1 (Synthesis of 2- (1-hydroxypentyl) -cyclopentan-1-one)
A 6m 3 reaction vessel equipped with a dripping vessel was charged with 2241 kg (26.6 kmol) of cyclopentanone, 1007 kg of water, and 11 kg of 48% NaOH, cooled to 15 ° C. with stirring, and then 985 kg (11. 4 kmol) was added dropwise over 5 hours, followed by stirring for 1 hour. After completion of the reaction, the reaction mixture was neutralized and excess cyclopentanone was recovered by distillation. The reaction product 1868 kg of the organic layer contained 1706 kg of 2- (1-hydroxypentyl) -cyclopentan-1-one.
製造例１（固体酸：ＥｔＰ−ＡｌＰＯ4の製造）
エチルホスホン酸（Ａｌｄｒｉｃｈ社製、純度９８％）９．９ｇと、８５％オルトリン酸（キシダ化学株式会社製）２７．７ｇ、硝酸アルミニウム（９水和物）（Ａｌｄｒｉｃｈ社製、純度９８％）１１２．５ｇを、水１０００ｇに溶解させた。室温にて、この混合溶液にアンモニア水溶液（キシダ化学株式会社製）を滴下し、ｐＨを５まで上昇させた。途中、ゲル状の白色沈殿が生成した。沈殿をろ過し、水洗後、１１０℃で１５時間乾燥した後、６０メッシュ以下に粉砕し、２５０℃で３時間焼成することにより、固体酸：ＥｔＰ−ＡｌＰＯ4を得た。
得られた固体酸について、ＩＣＰ発光分析装置（島津製作所製、ＩＣＰＳ１０００ＩＩＩ）、及びＣＨＮ元素分析装置（パーキンエルマー社製、２４００−２）を用いて、固体酸中の金属、リン及び炭素を測定した結果、金属１６％、リン１９％、炭素２．５％を含み、有機リン酸モル比ｘは０．１７であった。
Production Example 1 (Production of solid acid: EtP-AlPO 4 )
9.9 g of ethylphosphonic acid (manufactured by Aldrich, purity 98%), 27.7 g of 85% orthophosphoric acid (manufactured by Kishida Chemical Co., Ltd.), aluminum nitrate (9 hydrate) (manufactured by Aldrich, purity 98%) 112 0.5 g was dissolved in 1000 g of water. At room temperature, an aqueous ammonia solution (manufactured by Kishida Chemical Co., Ltd.) was added dropwise to this mixed solution to raise the pH to 5. On the way, a gel-like white precipitate was formed. The precipitate was filtered, washed with water, dried at 110 ° C. for 15 hours, pulverized to 60 mesh or less, and calcined at 250 ° C. for 3 hours to obtain a solid acid: EtP-AlPO 4 .
About the obtained solid acid, the metal, phosphorus, and carbon in a solid acid were measured using the ICP emission analyzer (the Shimadzu Corporation make, ICPS1000III) and the CHN elemental analyzer (the Perkin Elmer make, 2400-2). As a result, it contained 16% metal, 19% phosphorus and 2.5% carbon, and the organic phosphoric acid molar ratio x was 0.17.
また、得られた固体酸の酸点をアンモニア昇温脱離法（ＴＰＤ）によって測定〔測定装置；日本ベル株式会社製、マルチタスクＴＰＤ，測定条件；（前処理）ヘリウム中２００℃まで２０分で昇温、１時間保持、（ＮＨ3吸着処理）５０℃、２．７ｋＰａで１０分間ＮＨ3を吸着、（真空処理）５０℃、４時間処理、（ＴＰＤ測定）ヘリウムガスを５０ｍｌ／ｍｉｎで流通、昇温速度５℃／ｍｉｎで６００℃まで昇温。酸点の量は、触媒学会参照触媒であるゼオライト；ＪＲＣ−Ｚ５−２５Ｈのｈｉｇｈピーク（観測される２種のピークのうち、高温側のピーク）を０．９９ｍｍｏｌ／ｇとして、これに対する相対的な量として決定〕した結果、１００〜２５０℃においてアンモニアの脱離を起こす酸点の量は０．７４ｍｍｏｌ／ｇ、２５０℃より高い温度範囲でアンモニアの脱離を起こす酸点の量は０．０６ｍｍｏｌ／ｇであった。 In addition, the acid point of the obtained solid acid was measured by ammonia temperature programmed desorption method (TPD) [measuring device; manufactured by Nippon Bell Co., Ltd., multitask TPD, measurement conditions; 1 hour, (NH 3 adsorption treatment) 50 ° C., 2.7 kPa for 10 minutes, NH 3 adsorption (vacuum treatment) 50 ° C., 4 hours treatment, (TPD measurement) helium gas at 50 ml / min The temperature was raised to 600 ° C at a flow rate and a heating rate of 5 ° C / min. The amount of the acid sites is relative to the zeolite, which is a reference catalyst of the Catalysis Society of Japan; the high peak of JRC-Z5-25H (the peak on the high temperature side of the two observed peaks) is 0.99 mmol / g As a result, the amount of acid sites causing desorption of ammonia at 100 to 250 ° C. is 0.74 mmol / g, and the amount of acid points causing desorption of ammonia in a temperature range higher than 250 ° C. is 0. It was 06 mmol / g.
実施例１
（１）工程（Ａ）
脱水管を備えた２００ｍｌの４つ口セパラブルフラスコ（ガラス製）に、合成例１に記載の製造方法で得られた２−（１−ヒドロキシペンチル）−シクロペンタン−１−オン５０ｇ（純度８４％、０．２４７ｍｏｌ）、製造例１で調製した固体酸（形態：粉末）０．２０ｇ、５％Ｐｄ／Ｃ（Ｎ．Ｅ．ＣｈｅｍＣａｔ社製、Ｐｄカーボン粉末、４９％含水品、ｐＨ＝５．８）５．１ｇ（乾燥重量２．６ｇ）を加え、水素濃度２５容量％、窒素濃度７５容量％の混合ガスを、原料の２−（１−ヒドロキシペンチル）−シクロペンタン−１−オン純分１ｇあたり０．２Ｎ−ｍＬ／分の流量で反応液に吹き込みながら、１４０℃になるように加熱し混合し、温度が１４０℃に達した後３Ｈｒの反応を行なった。
（２）工程（Ｂ）
工程（Ａ）に続いて水素濃度１２．５容量％、窒素濃度８７．５容量％の混合ガスを、原料の２−（１−ヒドロキシペンチル）−シクロペンタン−１−オン純分１ｇあたり０．２Ｎ−ｍＬ／分の流量で反応液に吹き込みながら、１４０〜１４７℃（平均温度１４６℃）で１２Ｈｒの反応を行なった。
工程（Ｂ）終了後、反応終了物をＧＣにより定量した結果、２−ペンチル−２−シクロペンテン−１−オンが０．２１９ｍｏｌ生成し、２−ペンチルシクロペンタン−１−オンが０．０１２ｍｏｌ副生していた。２−ペンチル−２−シクロペンテン−１−オンの収率は８８．６％であった。その他の副生成物についての結果も纏めて表１に示す。
Example 1
(1) Step (A)
In a 200 ml four-necked separable flask (made of glass) equipped with a dehydrating tube, 50 g of 2- (1-hydroxypentyl) -cyclopentan-1-one obtained by the production method described in Synthesis Example 1 (purity 84 %, 0.247 mol), 0.20 g of solid acid prepared in Production Example 1 (form: powder), 5% Pd / C (manufactured by NE ChemCat, Pd carbon powder, 49% water-containing product, pH = 5 .8) 5.1 g (dry weight 2.6 g) was added, and a mixed gas having a hydrogen concentration of 25% by volume and a nitrogen concentration of 75% by volume was added to the raw material 2- (1-hydroxypentyl) -cyclopentan-1-one pure While blowing into the reaction solution at a flow rate of 0.2 N-mL / min per gram, the mixture was heated and mixed to 140 ° C., and the reaction was performed for 3 hours after the temperature reached 140 ° C.
(2) Process (B)
Subsequent to the step (A), a mixed gas having a hydrogen concentration of 12.5% by volume and a nitrogen concentration of 87.5% by volume was added to a raw material of 0.2 g per 1 g of pure 2- (1-hydroxypentyl) -cyclopentan-1-one. While blowing into the reaction solution at a flow rate of 2 N-mL / min, the reaction was performed at 140 to 147 ° C. (average temperature 146 ° C.) for 12 hours.
After completion of the step (B), the reaction end product was quantified by GC. As a result, 0.219 mol of 2-pentyl-2-cyclopenten-1-one was produced and 0.012 mol of 2-pentylcyclopentan-1-one was by-produced. Was. The yield of 2-pentyl-2-cyclopenten-1-one was 88.6%. The results for other by-products are also summarized in Table 1.
実施例２
（１）工程（Ａ）
脱水管を備えた２００ｍｌの４つ口セパラブルフラスコ（ガラス製）に、合成例１に記載の製造方法で得られた２−（１−ヒドロキシペンチル）−シクロペンタン−１−オン５０ｇ（純度８３％、０．２４４ｍｏｌ）、製造例１で調製した固体酸（形態：粉末）０．２０ｇ、前記５％Ｐｄ／Ｃ（Ｎ．Ｅ．ＣｈｅｍＣａｔ社製）５．１ｇ（乾燥重量２．６ｇ）を加え、水素濃度４０容量％、窒素濃度６０容量％の混合ガスを、原料の２−（１−ヒドロキシペンチル）−シクロペンタン−１−オン純分１ｇあたり０．２Ｎ−ｍＬ／分の流量で反応液に吹き込みながら、１４０℃になるように加熱し混合し、温度が１４０℃に達した後３Ｈｒの反応を行なった。
（２）工程（Ｂ）
工程（Ａ）に続いて水素濃度１２．５容量％、窒素濃度８７．５容量％の混合ガスを、原料の２−（１−ヒドロキシペンチル）−シクロペンタン−１−オン純分１ｇあたり０．２Ｎ−ｍＬ／分の流量で反応液に吹き込みながら、１４０〜１４７℃（平均温度１４６℃）で１０Ｈｒの反応を行なった。
工程（Ｂ）終了後、反応終了物をＧＣにより定量した結果、２−ペンチル−２−シクロペンテン−１−オンが０．２０９ｍｏｌ生成し、２−ペンチルシクロペンタン−１−オンが０．０１８ｍｏｌ副生していた。２−ペンチル−２−シクロペンテン−１−オンの収率は８５．６％であった。その他の副生成物についての結果も纏めて表１に示す。
Example 2
(1) Step (A)
In a 200 ml four-necked separable flask (made of glass) equipped with a dehydrating tube, 50 g of 2- (1-hydroxypentyl) -cyclopentan-1-one obtained by the production method described in Synthesis Example 1 (purity 83 %, 0.244 mol), 0.20 g of the solid acid prepared in Production Example 1 (form: powder), 5.1 g of 5% Pd / C (manufactured by NE ChemCat) (dry weight 2.6 g). In addition, a mixed gas having a hydrogen concentration of 40% by volume and a nitrogen concentration of 60% by volume is reacted at a flow rate of 0.2 N-mL / min per 1 g of 2- (1-hydroxypentyl) -cyclopentan-1-one pure component While being blown into the liquid, the mixture was heated and mixed to 140 ° C., and after the temperature reached 140 ° C., the reaction was performed for 3 hours.
(2) Process (B)
Subsequent to the step (A), a mixed gas having a hydrogen concentration of 12.5% by volume and a nitrogen concentration of 87.5% by volume was added to a raw material of 0.2 g per 1 g of pure 2- (1-hydroxypentyl) -cyclopentan-1-one. While blowing into the reaction solution at a flow rate of 2 N-mL / min, the reaction was performed at 140 to 147 ° C. (average temperature 146 ° C.) for 10 hours.
After completion of the step (B), the reaction end product was quantified by GC. As a result, 0.209 mol of 2-pentyl-2-cyclopenten-1-one was produced and 0.018 mol of 2-pentylcyclopentan-1-one was by-produced. Was. The yield of 2-pentyl-2-cyclopenten-1-one was 85.6%. The results for other by-products are also summarized in Table 1.
比較例１
（１）工程（Ａ）
脱水管を備えた２００ｍｌの４つ口セパラブルフラスコ（ガラス製）に、合成例１に記載の製造方法で得られた２−（１−ヒドロキシペンチル）−シクロペンタン−１−オン５０ｇ（純度８２％、０．２４２ｍｏｌ）、製造例１で調製した固体酸（形態：粉末）０．２０ｇ、前記５％Ｐｄ／Ｃ（Ｎ．Ｅ．ＣｈｅｍＣａｔ社製）５．１ｇ（乾燥重量２．６ｇ）を加え、水素濃度１００容量％のガスを、原料の２−（１−ヒドロキシペンチル）−シクロペンタン−１−オン純分１ｇあたり０．２Ｎ−ｍＬ／分の流量で反応液に吹き込みながら、１４０℃になるように加熱し混合し、温度が１４０℃に達した後２Ｈｒの反応を行なった。
（２）工程（Ｂ）
工程（Ａ）に続いて水素濃度５０容量％、窒素濃度５０容量％の混合ガスを、原料の２−（１−ヒドロキシペンチル）−シクロペンタン−１−オン純分１ｇあたり０．２Ｎ−ｍＬ／分の流量で反応液に吹き込みながら１４０℃で３Ｈｒの反応を行ない、更に水素濃度２０容量％、窒素濃度８０容量％の混合ガスを反応液に吹き込みながら、１４７℃で３Ｈｒの反応を行なった。
工程（Ｂ）終了後、反応終了物をＧＣにより定量した結果、２−ペンチル−２−シクロペンテン−１−オンが０．２００ｍｏｌ生成し、２−ペンチルシクロペンタン−１−オンが０．０３１ｍｏｌ副生していた。２−ペンチル−２−シクロペンテン−１−オンの収率は８２．８％であった。その他の副生成物についての結果も纏めて表１に示す。
Comparative Example 1
(1) Step (A)
In a 200 ml four-necked separable flask (made of glass) equipped with a dehydrating tube, 50 g of 2- (1-hydroxypentyl) -cyclopentan-1-one obtained by the production method described in Synthesis Example 1 (purity 82 %, 0.242 mol), 0.20 g of solid acid prepared in Production Example 1 (form: powder), 5.1 g of 5% Pd / C (manufactured by NE ChemCat) (dry weight 2.6 g). In addition, while blowing a gas having a hydrogen concentration of 100% by volume into the reaction solution at a flow rate of 0.2 N-mL / min per 1 g of pure 2- (1-hydroxypentyl) -cyclopentan-1-one raw material, The mixture was heated and mixed so that the temperature reached 140 ° C., and then the reaction was performed for 2 hours.
(2) Process (B)
Subsequent to the step (A), a mixed gas having a hydrogen concentration of 50 vol% and a nitrogen concentration of 50 vol% is mixed with 0.2 N-mL / g of pure 2- (1-hydroxypentyl) -cyclopentan-1-one as a raw material The reaction was conducted for 3 hours at 140 ° C. while blowing into the reaction solution at a flow rate of minutes, and further, the reaction was carried out for 3 hours at 147 ° C. while blowing a mixed gas having a hydrogen concentration of 20 vol% and a nitrogen concentration of 80 vol% into the reaction solution.
After completion of the step (B), the reaction end product was quantified by GC. As a result, 0.200 mol of 2-pentyl-2-cyclopenten-1-one was produced and 0.031 mol of 2-pentylcyclopentan-1-one was by-produced. Was. The yield of 2-pentyl-2-cyclopenten-1-one was 82.8%. The results for other by-products are also summarized in Table 1.
比較例２
（１）工程（Ａ）
脱水管を備えた２００ｍｌの４つ口セパラブルフラスコ（ガラス製）に、合成例１に記載の製造方法で得られた２−（１−ヒドロキシペンチル）−シクロペンタン−１−オン５０ｇ（純度８３％、０．２４４ｍｏｌ）、製造例１で調製した固体酸（形態：粉末）０．２０ｇ、前記５％Ｐｄ／Ｃ（Ｎ．Ｅ．ＣｈｅｍＣａｔ社製）５．１ｇ（乾燥重量２．６ｇ）を加え、水素濃度５０容量％、窒素濃度５０容量％の混合ガスを、原料の２−（１−ヒドロキシペンチル）−シクロペンタン−１−オン純分１ｇあたり０．２Ｎ−ｍＬ／分の流量で反応液に吹き込みながら、１４０℃になるように加熱し混合し、温度が１４０℃に達した後３Ｈｒの反応を行なった。
（２）工程（Ｂ）
工程（Ａ）に続いて水素濃度１２．５容量％、窒素濃度８７．５容量％の混合ガスを、原料の２−（１−ヒドロキシペンチル）−シクロペンタン−１−オン純分１ｇあたり０．２Ｎ−ｍＬ／分の流量で反応液に吹き込みながら１４０℃〜１４７℃（平均温度１４５℃）で９Ｈｒの反応を行なった。
工程（Ｂ）終了後、反応終了物をＧＣにより定量した結果、２−ペンチル−２−シクロペンテン−１−オンが０．２０５ｍｏｌ生成し、２−ペンチルシクロペンタン−１−オンが０．０２２ｍｏｌ副生していた。２−ペンチル−２−シクロペンテン−１−オンの収率は８４．３％であった。その他の副生成物についての結果も纏めて表１に示す。
Comparative Example 2
(1) Step (A)
In a 200 ml four-necked separable flask (made of glass) equipped with a dehydrating tube, 50 g of 2- (1-hydroxypentyl) -cyclopentan-1-one obtained by the production method described in Synthesis Example 1 (purity 83 %, 0.244 mol), 0.20 g of the solid acid prepared in Production Example 1 (form: powder), 5.1 g of 5% Pd / C (manufactured by NE ChemCat) (dry weight 2.6 g). In addition, a mixed gas having a hydrogen concentration of 50 vol% and a nitrogen concentration of 50 vol% is reacted at a flow rate of 0.2 N-mL / min per 1 g of pure 2- (1-hydroxypentyl) -cyclopentan-1-one as a raw material. While being blown into the liquid, the mixture was heated and mixed to 140 ° C., and after the temperature reached 140 ° C., the reaction was performed for 3 hours.
(2) Process (B)
Subsequent to the step (A), a mixed gas having a hydrogen concentration of 12.5% by volume and a nitrogen concentration of 87.5% by volume was added to a raw material of 0.2 g per 1 g of pure 2- (1-hydroxypentyl) -cyclopentan-1-one. While blowing into the reaction solution at a flow rate of 2 N-mL / min, the reaction was performed at 140 ° C. to 147 ° C. (average temperature 145 ° C.) for 9 hours.
After completion of the step (B), the reaction end product was quantified by GC. As a result, 0.205 mol of 2-pentyl-2-cyclopenten-1-one was produced and 0.022 mol of 2-pentylcyclopentan-1-one was by-produced. Was. The yield of 2-pentyl-2-cyclopenten-1-one was 84.3%. The results for other by-products are also summarized in Table 1.
比較例３
脱水管を備えた２００ｍｌの４つ口セパラブルフラスコに、合成例１に記載の製造方法で得られた２−（１−ヒドロキシペンチル）−シクロペンタン−１−オン５０．８ｇ（純度８１％、０．２４３ｍｏｌ）、製造例１で調製した固体酸（形態：粉末）０．１３ｇ、前記５％Ｐｄ／Ｃ（Ｎ．Ｅ．ＣｈｅｍＣａｔ社製）５．０ｇ（乾燥重量２．６ｇ）を加え、水素濃度１２．５容量％、窒素濃度８７．５容量％の混合ガスを、原料の２−（１−ヒドロキシペンチル）−シクロペンタン−１−オン純分１ｇあたり０．２Ｎ−ｍＬ／分の流量で反応液に吹き込みながら１５０℃になるように加熱し混合した。
温度が１５０℃に達した反応開始から１５．５時間後には、留分が７．８１ｇ得られ、反応終了物をＧＣにより定量した結果、２−ペンチル−２−シクロペンテン−１−オン３１．４ｇ（０．２０６ｍｏｌ）、２−ペンチルシクロペンタン−１−オン１．５ｇ（０．０１０ｍｏｌ）が生成していた。２−ペンチル−２−シクロペンテン−１−オンの収率は８５．０％であった。その他の副生成物についての結果も纏めて表１に示す。
Comparative Example 3
In a 200 ml four-necked separable flask equipped with a dehydrating tube, 50.8 g of 2- (1-hydroxypentyl) -cyclopentan-1-one obtained by the production method described in Synthesis Example 1 (purity 81%, 0.243 mol), 0.13 g of the solid acid prepared in Production Example 1 (form: powder), 5.0 g of 5% Pd / C (manufactured by NE ChemCat) (dry weight 2.6 g), A flow rate of 0.2 N-mL / min of a mixed gas having a hydrogen concentration of 12.5% by volume and a nitrogen concentration of 87.5% by volume per 1 g of pure 2- (1-hydroxypentyl) -cyclopentan-1-one as a raw material The mixture was heated and mixed to 150 ° C. while being blown into the reaction solution.
After 15.5 hours from the start of the reaction when the temperature reached 150 ° C., 7.81 g of a fraction was obtained, and the reaction end product was quantified by GC. As a result, 31.4 g of 2-pentyl-2-cyclopenten-1-one was obtained. (0.206 mol), 1.5 g (0.010 mol) of 2-pentylcyclopentan-1-one was produced. The yield of 2-pentyl-2-cyclopenten-1-one was 85.0%. The results for other by-products are also summarized in Table 1.
実施例３
（１）工程（Ａ）
脱水管を備えた２０００ｍｌの４つ口セパラブルフラスコ（ガラス製）に、合成例１に記載の製造方法で得られた２−（１−ヒドロキシペンチル）−シクロペンタン−１−オン１３９５ｇ（純度８５％、６．９５ｍｏｌ）、製造例１で調製した固体酸（形態：粉末）３．６ｇ、５％Ｐｄ／Ｃ(エボニック デグサ ジャパン社製、粉末、６８．６％含水品）１３３．３ｇ（乾燥重量４１．９ｇ）を加え、水素濃度１２．５容量％、窒素濃度８７．５容量％の混合ガスを、原料の２−（１−ヒドロキシペンチル）−シクロペンタン−１−オン純分１ｇあたり０．２Ｎ−ｍＬ／分の流量で反応液に吹き込みながら、１４０℃になるように加熱し混合し、温度が１４０℃に達した後７Ｈｒの反応を行なった。
（２）工程（Ｂ）
工程（Ａ）に続いて水素濃度７．５容量％、窒素濃度９２．５容量％の混合ガスを、原料の２−（１−ヒドロキシペンチル）−シクロペンタン−１−オン純分１ｇあたり０．２Ｎ−ｍＬ／分の流量で反応液に吹込みながら、１５０℃で７Ｈｒの反応を行なった。
工程（Ｂ）終了後、反応終了物をＧＣにより定量した結果、２−ペンチル−２−シクロペンテン−１−オンが６．１３ｍｏｌ生成し、２−ペンチルシクロペンタン−１−オンが０．３０ｍｏｌ副生していた。２−ペンチル−２−シクロペンテン−１−オンの収率は８８．１％であった。その他の副生成物についての結果も纏めて表１に示す。
Example 3
(1) Step (A)
In a 2000 ml four-necked separable flask (made of glass) equipped with a dehydrating tube, 1395 g of 2- (1-hydroxypentyl) -cyclopentan-1-one obtained by the production method described in Synthesis Example 1 (purity 85 %, 6.95 mol), solid acid (form: powder) prepared in Production Example 1 3.6 g, 5% Pd / C (Evonik Degussa Japan, powder, 68.6% water-containing product) 133.3 g (dry) 41.9 g in weight), and a mixed gas having a hydrogen concentration of 12.5% by volume and a nitrogen concentration of 87.5% by volume was added to the raw material 2- (1-hydroxypentyl) -cyclopentan-1-one per 1 g of pure component. While being blown into the reaction solution at a flow rate of 2 N-mL / min, the mixture was heated and mixed to 140 ° C., and the reaction was carried out for 7 hours after the temperature reached 140 ° C.
(2) Process (B)
Subsequent to the step (A), a mixed gas having a hydrogen concentration of 7.5 vol% and a nitrogen concentration of 92.5 vol% was added to the raw material 2- (1-hydroxypentyl) -cyclopentan-1-one in an amount of 0. While blowing into the reaction solution at a flow rate of 2 N-mL / min, the reaction was carried out at 150 ° C. for 7 hours.
After completion of the step (B), the reaction end product was quantified by GC. As a result, 6.13 mol of 2-pentyl-2-cyclopenten-1-one was produced and 0.30 mol of 2-pentylcyclopentan-1-one was by-produced. Was. The yield of 2-pentyl-2-cyclopenten-1-one was 88.1%. The results for other by-products are also summarized in Table 1.
比較例４
（１）工程（Ａ）
脱水管を備えた２０００ｍｌの４つ口セパラブルフラスコ（ガラス製）に、合成例１に記載の製造方法で得られた２−（１−ヒドロキシペンチル）−シクロペンタン−１−オン１３９５ｇ（純度８５％、６．９５ｍｏｌ）、製造例１で調製した固体酸（形態：粉末）３．６ｇ、５％Ｐｄ／Ｃ（エボニック デグサ ジャパン社製、粉末、４９％含水品）１３３．３ｇ（乾燥重量４１．９ｇ）を加え、水素濃度１２．５容量％、窒素濃度８７．５容量％の混合ガスを、原料の２−（１−ヒドロキシペンチル）−シクロペンタン−１−オン純分１ｇあたり０．２Ｎ−ｍＬ／分の流量で反応液に吹き込みながら、１４０℃になるように加熱し混合し、温度が１４０℃に達した後７Ｈｒの反応を行なった。
（２）工程（Ｂ）
工程（Ａ）に続いて窒素ガスのみを、原料の２−（１−ヒドロキシペンチル）−シクロペンタン−１−オン純分１ｇあたり０．２Ｎ−ｍＬ／分の流量で反応液に吹き込みながら、１５０℃で１５Ｈｒの反応を行なった。
工程（Ｂ）終了後、反応終了物をＧＣにより定量した結果、２−ペンチル−２−シクロペンテン−１−オンが３．４３ｍｏｌ生成し、２−ペンチルシクロペンタン−１−オンが０．１４ｍｏｌ副生していた。２−ペンチル−２−シクロペンテン−１−オンの収率は４９．３％であった。その他の副生成物についての結果も纏めて表１に示す。
Comparative Example 4
(1) Step (A)
In a 2000 ml four-necked separable flask (made of glass) equipped with a dehydrating tube, 1395 g of 2- (1-hydroxypentyl) -cyclopentan-1-one obtained by the production method described in Synthesis Example 1 (purity 85 %, 6.95 mol), solid acid (form: powder) prepared in Production Example 1 3.6 g, 5% Pd / C (Evonik Degussa Japan, powder, 49% water-containing product) 133.3 g (dry weight 41) 0.9 g), and a mixed gas having a hydrogen concentration of 12.5% by volume and a nitrogen concentration of 87.5% by volume was added to 0.2 N per 1 g of pure 2- (1-hydroxypentyl) -cyclopentan-1-one as a raw material. While blowing into the reaction solution at a flow rate of −mL / min, the mixture was heated and mixed to 140 ° C., and the reaction was carried out for 7 hours after the temperature reached 140 ° C.
(2) Process (B)
Following the step (A), only nitrogen gas was blown into the reaction solution at a flow rate of 0.2 N-mL / min per 1 g of the raw material 2- (1-hydroxypentyl) -cyclopentan-1-one. The reaction was performed at 15 ° C. for 15 hours.
After completion of the step (B), the reaction end product was quantified by GC. As a result, 3.43 mol of 2-pentyl-2-cyclopenten-1-one was produced and 0.14 mol of 2-pentylcyclopentan-1-one was by-produced. Was. The yield of 2-pentyl-2-cyclopenten-1-one was 49.3%. The results for other by-products are also summarized in Table 1.
表１の脚注を以下に示す。
１）触媒量＝（乾燥状態の触媒質量）／（原料質量）×１００
２）収率＝（反応物中の２−ペンチル−２−シクロペンテン−１−オンのモル数）／（原料中の２−（１−ヒドロキシペンチル）−シクロペンタン−１−オンのモル数）×１００
３）飽和体量＝（反応物中の２−ペンチルシクロペンタン−１−オンのモル数）／（原料中の２−（１−ヒドロキシペンチル）−シクロペンタン−１−オンのモル数）×１００
４）その他副生物量＝（反応物中の２−ペンチルシクロペンタン−１−オン以外の副反応物モル数）／（原料中の２−（１−ヒドロキシペンチル）−シクロペンタン−１−オンのモル数）×１００
The footnotes in Table 1 are shown below.
1) Catalyst amount = (dry catalyst mass) / (raw material mass) × 100
2) Yield = (mole number of 2-pentyl-2-cyclopenten-1-one in the reaction product) / (mole number of 2- (1-hydroxypentyl) -cyclopentan-1-one in the raw material) × 100
3) Saturated substance amount = (number of moles of 2-pentylcyclopentan-1-one in the reaction product) / (number of moles of 2- (1-hydroxypentyl) -cyclopentan-1-one in the raw material) × 100
4) Amount of other by-products = (number of moles of by-products other than 2-pentylcyclopentan-1-one in the reaction product) / (of 2- (1-hydroxypentyl) -cyclopentan-1-one in the raw material) Number of moles) x 100
Claims (4)
工程（Ａ）：水素ガス濃度５〜４５容量％の雰囲気下で脱水異性化させる工程
工程（Ｂ）：水素ガス濃度１容量％以上、かつ工程（Ａ）における水素濃度よりも２容量％以上低い濃度の雰囲気下で脱水異性化させる工程
Step (A): Step of dehydration isomerization in an atmosphere having a hydrogen gas concentration of 5 to 45% by volume Step (B): Hydrogen gas concentration of 1% by volume or more and 2% by volume or more lower than the hydrogen concentration in step (A) Dehydration isomerization process in a concentration atmosphere
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| JPH0592934A (en) * | 1991-09-30 | 1993-04-16 | Nippon Zeon Co Ltd | Production of 2-alkyl-2-cycloalkene-1-one compounds |
| JP2001328965A (en) * | 2000-03-15 | 2001-11-27 | Kao Corp | Method for producing jasmonate derivative and intermediate thereof |
| JP2004203844A (en) * | 2002-12-26 | 2004-07-22 | Kao Corp | Method for production of 2-(alkylidene)cycloalkanone |
| JP2004217620A (en) * | 2002-12-26 | 2004-08-05 | Kao Corp | Method for producing 2-(alkyl)cycloalkenone |
| JP2009078983A (en) * | 2007-09-25 | 2009-04-16 | Nippon Zeon Co Ltd | Continuous preparation method for 2-alkylidene cycloalkanone |
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| JPH0592934A (en) * | 1991-09-30 | 1993-04-16 | Nippon Zeon Co Ltd | Production of 2-alkyl-2-cycloalkene-1-one compounds |
| JP2001328965A (en) * | 2000-03-15 | 2001-11-27 | Kao Corp | Method for producing jasmonate derivative and intermediate thereof |
| JP2004203844A (en) * | 2002-12-26 | 2004-07-22 | Kao Corp | Method for production of 2-(alkylidene)cycloalkanone |
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